CN106675524A - Multifunctional phase change material microcapsule and preparation method thereof - Google Patents
Multifunctional phase change material microcapsule and preparation method thereof Download PDFInfo
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- CN106675524A CN106675524A CN201610552024.7A CN201610552024A CN106675524A CN 106675524 A CN106675524 A CN 106675524A CN 201610552024 A CN201610552024 A CN 201610552024A CN 106675524 A CN106675524 A CN 106675524A
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- Prior art keywords
- change material
- phase change
- capsule
- microcapsule
- phase
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 83
- 239000012782 phase change material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 35
- 230000008859 change Effects 0.000 claims abstract description 30
- 239000012074 organic phase Substances 0.000 claims abstract description 20
- 239000012071 phase Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 10
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 fatty acid ester Chemical class 0.000 claims abstract description 7
- 239000000839 emulsion Substances 0.000 claims abstract description 6
- 239000012188 paraffin wax Substances 0.000 claims abstract description 6
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000002775 capsule Substances 0.000 claims description 15
- 238000004146 energy storage Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000011258 core-shell material Substances 0.000 claims description 8
- 230000005070 ripening Effects 0.000 claims description 8
- 239000011232 storage material Substances 0.000 claims description 8
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 7
- LBJNMUFDOHXDFG-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu].[Cu] LBJNMUFDOHXDFG-UHFFFAOYSA-N 0.000 claims description 7
- 239000008103 glucose Substances 0.000 claims description 7
- 150000002191 fatty alcohols Chemical class 0.000 claims description 6
- 125000001931 aliphatic group Chemical group 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002736 nonionic surfactant Substances 0.000 claims description 2
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 2
- 229920000053 polysorbate 80 Polymers 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 235000011067 sorbitan monolaureate Nutrition 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- 239000002202 Polyethylene glycol Substances 0.000 claims 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims 1
- 125000002091 cationic group Chemical group 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229920001223 polyethylene glycol Polymers 0.000 claims 1
- 229910052938 sodium sulfate Inorganic materials 0.000 claims 1
- 235000011152 sodium sulphate Nutrition 0.000 claims 1
- 239000001993 wax Substances 0.000 claims 1
- 235000014113 dietary fatty acids Nutrition 0.000 abstract description 6
- 239000000194 fatty acid Substances 0.000 abstract description 6
- 229930195729 fatty acid Natural products 0.000 abstract description 6
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 150000004665 fatty acids Chemical class 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 239000010865 sewage Substances 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract 2
- 229910001431 copper ion Inorganic materials 0.000 abstract 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical group [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract 2
- 229940112669 cuprous oxide Drugs 0.000 abstract 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 abstract 1
- 241000894006 Bacteria Species 0.000 abstract 1
- 239000003513 alkali Substances 0.000 abstract 1
- 239000011162 core material Substances 0.000 abstract 1
- 239000003814 drug Substances 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 238000001556 precipitation Methods 0.000 abstract 1
- 238000006479 redox reaction Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 230000035945 sensitivity Effects 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 230000004044 response Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000007704 transition Effects 0.000 description 7
- 238000013019 agitation Methods 0.000 description 6
- 238000000113 differential scanning calorimetry Methods 0.000 description 6
- 230000001804 emulsifying effect Effects 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 241000287882 Pavo Species 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229940107698 malachite green Drugs 0.000 description 4
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229940002712 malachite green oxalate Drugs 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000000052 vinegar Substances 0.000 description 3
- 235000021419 vinegar Nutrition 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004566 building material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010068052 Mosaicism Diseases 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000005338 heat storage Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 210000003765 sex chromosome Anatomy 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004736 wide-angle X-ray diffraction Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- B01J35/39—
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
Abstract
The invention discloses a multifunctional phase change material microcapsule and a preparation method thereof and belongs to the technical field of phase change materials. A wall material of the microcapsule is cuprous oxide with photocatalysis function and gas sensitive property; a core material comprises paraffin, higher fatty acid organic phase change materials, higher aliphatic alcohol organic phase change materials, higher fatty acid ester organic phase change materials. The preparation method of the multifunctional phase change material microcapsule comprises the following steps: dispersing organic phase change materials and surfactants in water phase to form an emulsion, then adding a copper source, and adsorbing copper ions to surfaces of phase change material emulsion particles through interaction between ions; adding alkali and reducing agents, and achieving redox reaction on the copper ions on the surface of the microcapsule through an interfacial precipitation method so as to obtain the microcapsule with the phase change materials coated with cuprous oxide. The microcapsule has functions of storing latent heat and regulating the temperature; the wall material also has multiple functions of catalyzing visible light, sensing gas, resisting bacteria and improving performance of lithium ion batteries, and can be widely applied to the fields of sewage treatment, gas sensors, medicine and lithium ion batteries.
Description
Technical field
The present invention relates to a kind of phase-change material micro-capsule, more particularly to one kind is with visible light catalytic effect and gas-sensitive property
Multi-functional organic phase change material microcapsule and preparation method thereof, belong to phase-change material technical field.
Background technology
Continuous exploitation of the mankind to Fossil fuel raw material not only makes storage capacity of these fossil energies in the earth's crust continuous
Decline, and also create very serious problem of environmental pollution, especially considerably increase the discharge capacity of carbon dioxide, cause
Global Greenhouse Effect, to the environment of human living very ill effect is caused.And as the size of population is continuously increased, to energy
The demand in source is also constantly going up, and present energy crisis has become the whole world all problem demanding prompt solutions.In order to solve the energy
Shortage and clean energy sex chromosome mosaicism, further realize sustainable development, and scientists propose two kinds of effective and feasible solution party
Method：(1) regenerative resource is developed, including a series of regenerative resources such as solar energy, wind energy, tide energy, nuclear energy, (2) improve energy
The utilization ratio in source, solves the energy unmatched problem over time and space, and the research of phase-change material micro-capsule is exactly to pass through
The method of thermal energy storage is improving the utilization ratio of the energy.
So-called " phase-change material ", refers at a certain temperature by crystallization or melting, i.e., by the change of phase, realize
The storage or release of latent heat energy, while keeping temperature does not change within the specific limits in phase transition process.Phase-change material
According to the difference of phase transformation mode can be divided into " solid-solid " phase-change material, " solid-liquid " phase-change material, " liquid-vapour " phase-change material and
" Gu-vapour " phase-change material.Because being limited to category and price, the development and application of " solid-solid " material is not extensive；And " liquid-
Vapour " phase-change material and " Gu-vapour " phase-change material also do not have and preferably answer because change in volume is big in phase transition process, difficult control
Use prospect；" solid-liquid " phase-change material is because cheap, species is various, phase transition process change in volume is ground the features such as little
The persons of studying carefully widely study.Common " solid-liquid " phase-change material includes organic paraffin, higher aliphatic acids, senior class fatty alcohols
With higher fatty acids esters etc..Phase-change material can adjust temperature, storage energy, can be widely used in energy-saving building material, cold accumulating
The field such as defeated, intelligent fiber and military infrared stealth.But phase-change material is susceptible to leak in use, pollutes environment
A series of problems, such as, in order to solve this problem, phase-change material micro-capsule operation and give birth to.
Phase-change material micro-capsule can effectively solve the problem that leakage and problem of environmental pollution, and at present disclosed data shows, closes
In the research of organic phase change energy storage material microcapsule, how its emphasis improves the state control of phase-change material, has if mainly being studied
Effect improves its energy storage efficiency, seldom relates to specific physical chemistry effect for possessing using microcapsule wall material to expand micro- glue
The function and application of capsule.In fact many inorganic material not only have anti-flammability, high intensity, high-termal conductivity and permeability resistance
Strong the characteristics of, while the specific physical chemical efficiencies such as characteristic of semiconductor, photoelectricity magnetic characteristic, antibiotic property and photocatalytic are also equipped with,
This phase-change material micro-capsule for allowing for inorganic wall material cladding not only has the function of phase-change accumulation energy, while being also equipped with above-mentioned
Special efficacy.The A of Chinese patent CN 103992774 are disclosed with magnetic ferrites/silicon dioxide compound wall materialses cladding positive 20
The technology of preparing of alkane phase-change material micro-capsule, the microcapsule has magnetic and thermal energy storage function concurrently.Chinese patent CN
103980864 A disclose the organic phase change material based on crystallized zirconia wall material or element doping crystallized zirconia wall material
The synthetic method of microcapsule, while being characterized in that the microcapsule possesses energy-saving and temperature-regulating effect, illustrates the spy of luminescence generated by light again
Property.And the A of Chinese patent CN 105238361 are disclosed and are prepared microcapsule with silver/silicon dioxide bilayer wall material surrounding phase change material
Synthetic technology, be the double function characteristic for possessing energy storage and antibacterial ability the characteristics of the microcapsule.Chinese patent CN
103992773 A are then disclosed with crystalline titanic oxide as wall material, AI3-28404 as phase-change material, prepare have photocatalysis work(
The technological invention of the difunctional phase-change material micro-capsule of effect.
Above-mentioned Chinese patent all employs inorganic functional material as wall material to synthesize difunctional phase-change material micro-capsule,
So that microcapsule is while possessing energy-saving and temperature-regulating function, various specific physical chemistry effects are also equipped with.Therefore, using nothing
Specific physical chemistry effect that machine material itself possesses is preparing the micro- glue of inorganic functional wall material cladding organic phase change material
Capsule, can give phase-change material micro-capsule more functions, with these New-type bifunctionals or multi-functional phase-change material micro-capsule
Successful exploitation, will also expand application of the phase-change material in more high-grade, precision and advanced fields.
The content of the invention
The present invention is based on coating organic phase change material using inorganic functional wall material, so as to prepare with specific physico
Learn the design philosophy of the difunctional phase-change material micro-capsule of effect, adopt there is the Red copper oxide of photocatalytic and gas-sensitive property for
Wall material coating organic phase change material, develop it is a kind of both there is phase-change accumulation energy and temperature adjustment function, have visible light catalytic work(concurrently again
The multi-functional phase-change material micro-capsule of effect and gas sensing property.
A kind of multi-functional phase-change material micro-capsule, capsule core is organic phase change energy storage material, and species is organic paraffin, senior
One or more in fatty acid, senior class fatty alcohols and high-grade aliphatic ester class phase transformation energy storage material, capsule shells are oxidation
Cuprous, its structure is typical " core-shell structure copolymer " structure；The mass percent of microcapsule total quality shared by capsule core be 20~
60wt.%, the mass percent of microcapsule total quality shared by capsule shells is 40~80wt.%；Its capsule grain diameter be 0.5~
5.0μm。
The crystalline form of capsule shells Red copper oxide capsule shells is simple Emission in Cubic, and with ultraviolet light and visible light catalytic effect
And gas-sensitive property.
The preparation method of a kind of multi-functional phase-change material micro-capsule proposed by the invention, can by following technological means and
Processing step is realizing：
(1) in the case where temperature is for 40~80 DEG C, by surfactant, quality that weight/mass percentage composition is 1.2~5.3wt.%
Percentage composition is the deionization that the organic phase change material and weight/mass percentage composition of 2.2~4.7wt.% is 90.0~96.6wt.%
Water mixes, and 1~3h is stirred under the rotating speed of 250~450rpm, obtains uniform and stable organic phase change material emulsion.
(2) under conditions of maintaining said temperature and stir speed (S.S.) constant, copper source aqueous solution is added to into step (1) made
In standby organic phase change material emulsion, at a temperature of 40~80 DEG C, 1~3h is reacted, then again simultaneously Deca sodium hydroxide is water-soluble
Liquid and reducing agent aqueous solution, keeping temperature and stir speed (S.S.) it is constant, continue react 4~6h after, stop stirring, 6~8h of ripening, use
Deionized water wash product 3~5 times, then filters, spontaneously dries, you can obtain multi-functional phase-change material micro-capsule.
In above-mentioned steps (2), the raw material composition of preferred reaction system and mass percent are：
Surfactant is cationic surfactant or nonionic surfactant in above-mentioned steps (1), wherein excellent
Select cetyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride, sodium lauryl sulphate, PVP, poly-
One or more in ethylene glycol, span20, tween80.
Organic phase change material in above-mentioned steps (1) preferably organic paraffin, higher aliphatic acids, senior class fatty alcohols and height
One or more in level fatty acid ester phase-changing energy storage material.
Copper source is the one kind in Schweinfurt green, copper sulfate and copper chloride, the mass percent of its aqueous solution in above-mentioned steps (2)
Concentration is 6.2~13.8wt.%.
Reducing agent is the one kind in sodium sulfite, glucose, hydrazine hydrate, ascorbic acid, its aqueous solution in above-mentioned steps (2)
Mass percent concentration be 3.3~14.3wt.%.
The concentration of sodium hydrate aqueous solution is 2~4mol/L in above-mentioned steps (2).
The present invention compared with prior art, with property effect following prominent：
(1) defect of the simple function of conventional phase change material microcapsule is breached, many of phase-change material micro-capsule are realized
Functionalization.The phase-change material micro-capsule invented not only possesses good hidden heat energy storage and homoiothermic work(function, and being also equipped with can
See photocatalysis effect and gas-sensitive property, this multifunction design can be such that the application of phase-change material micro-capsule obtains further
Expand so as to suitable for fields such as energy-saving building material, temperature-regulating fiber, photocatalyst, gas sensor, sewage disposals.
(2) breaching the inorganic catalysis material such as traditional titanium dioxide can only implement photodegradative office by absorbing ultraviolet light
Limit, the microcapsule can utilize the visible light catalytic characteristic that its Red copper oxide shell possesses, and be capable of achieving under the conditions of natural light to having
The light degradation of machine thing, so as to improve the utilization rate of sunlight, this feature is especially advantageous for its application in sewage treatment area.
(3) the Red copper oxide housing of the microcapsule has to toxic and harmfuls such as ethanol, acetone, nitrogen dioxide, hydrogen sulfide
Air-sensitive features of response, it has wide practical use on gas sensor.
Description of the drawings
The electron scanning micrograph of the multi-functional phase-change material micro-capsules of Fig. 1；
The transmission electron microscope photo of the multi-functional phase-change material micro-capsules of Fig. 2；
The means of differential scanning calorimetry spectrogram of the multi-functional phase-change material micro-capsules of Fig. 3；
The X-ray diffraction spectrogram of the multi-functional phase-change material micro-capsules of Fig. 4；
The multi-functional phase-change material micro-capsules of Fig. 5 change over curve to the sun photodegradation rate of malachite green oxalate；
Air-sensitive response cycle curve of the multi-functional phase-change material micro-capsules of Fig. 6 to ethanol three times.
Specific embodiment
Further illustrate the present invention with accompanying drawing with reference to embodiments.Following embodiments are based on before technical solution of the present invention
Put what is implemented, there is provided detailed synthetic method and implementation process；But protection scope of the present invention is not limited to following realities
Example is applied, following examples of the present invention illustrate that the phase-change material of the present invention can be adopted using AI3-28404 as phase-change material example
Existing conventional any organic phase change material, preferably organic paraffin, higher aliphatic acids, senior class fatty alcohols and higher fatty acids
One or more in esters phase-changing energy storage material.
Embodiment 1
First by 2.4g AI3-28404,1.578g cetyl trimethylammonium bromide and 50mL deionized waters add 250mL
There-necked flask in, in 60 DEG C of oil bath pan, with the mechanical agitation speed emulsifying 1h of 300rpm.It is by 30mL concentration
The copper-bath fast drop of 0.5mol/L in there-necked flask, after 1.5h, by the 30mL concentration being configured
It is that 2.5mol/L sodium hydroxide solutions and 30mL concentration are dropwise added drop-wise in there-necked flask for the glucose solution of 0.28mol/L,
Reaction 5h, stops stirring, and then 6~8h of ripening, deionized water flushing product 3~5 times filters, is dried, and obtains multi-functional photograph
Become material microcapsule.Electron scanning micrograph such as Fig. 1 institutes of multi-functional phase-change material micro-capsule prepared by present embodiment
Show, it can be found that the particle diameter of prepared multi-functional phase-change material micro-capsule is between 0.5~5 μm, uniform particle sizes.This embodiment party
The transmission electron microscope photo of multi-functional phase-change material micro-capsule prepared by formula is as shown in Fig. 2 it can be found that prepared is more
Function phase-change material micro-capsule has perfect " core-shell structure copolymer " structure.Multi-functional phase-change material micro-capsule prepared by present embodiment
After differential scanning calorimeter test, its heat flow versus temperature curve to curve in Fig. 3 as shown in figure 3, be integrated available
The melting enthalpy and crystallization enthalpy of the multi-functional phase-change material micro-capsule is respectively 168.1J/g and 169.7J/g, and clad ratio is
62.91%, with good latent heat storage-release performance.Multi-functional phase-change material micro-capsule prepared by present embodiment is passed through
After Wide angle X-ray diffraction test, its X-ray diffraction spectrogram model as shown in Figure 4, the characteristic peak in spectrogram is sharp, miscellaneous without other
Peak, peak value correspondence numerical value shows that the crystal formation of Red copper oxide is simple cubic phase.Multi-functional phase-change material prepared by present embodiment
Microcapsule through sunlight light degradation malachite green oxalate test, its degradation rate over time as shown in figure 5, through 140min it
Degradation rate afterwards is 90.68%.Multi-functional phase-change material micro-capsule prepared by present embodiment tests the microcapsule to ethanol 3
Secondary air-sensitive response is as shown in fig. 6, wherein concentration of alcohol is 50ppm, RaRepresent the aerial resistance value of microcapsule, RgTable
Show resistance value of the microcapsule in test gas, S represents sensitivity, and the sensitivity that the microcapsule is tested at 100 DEG C is 1.68,
And the sensitivity after 3 loop tests does not decline.
Embodiment 2
First by 3.2g AI3-28404,1.578g cetyl trimethylammonium bromide and 50mL water add three mouthfuls of 250mL
In flask, in 60 DEG C of oil bath pan, with the mechanical agitation speed emulsifying 1h of 300rpm.By the sulfur that 30mL concentration is 0.5mol/L
The 30mL concentration being configured is 2.5mol/L hydrogen after 1.5h in there-necked flask by sour copper solution fast drop
Sodium hydroxide solution and 30mL concentration are dropwise added drop-wise in there-necked flask for the glucose solution of 0.28mol/L, react 5h, stop stirring
Mix, 6~8h of ripening, then deionized water flushing product 3~5 times filters, is dried, and obtains multi-functional phase-change material micro-capsule,
Its surface compact is smooth, with " core-shell structure copolymer " structure.Obtaining the phase transition temperature of the microcapsule through means of differential scanning calorimetry test is
32.1 DEG C and 38.7 DEG C, enthalpy of phase change is 147.9~148.5J/g；In light degradation experiment, after 140min solar irradiations, peafowl
Malachite green degradation rate is 87.56%；Tested by gas sensing property, after its result shows the microcapsule to the air-sensitive response of ethanol 3 times
Sensitivity does not decline, and its sensitivity is 1.23.
Embodiment 3
First by 2.4g AI3-28404,1.578g cetyl trimethylammonium bromide and 50mL water add three mouthfuls of 250mL
In flask, in 60 DEG C of oil bath pan, with the mechanical agitation speed emulsifying 1h of 300rpm.By the vinegar that 30mL concentration is 0.5mol/L
The 30mL concentration being configured is 2.5mol/L hydrogen after 1.5h in there-necked flask by sour copper solution fast drop
Sodium hydroxide solution and 30mL concentration are dropwise added drop-wise in there-necked flask for the glucose solution of 0.28mol/L, react 5h, stop stirring
Mix, 6~8h of ripening, then deionized water flushing product 3~5 times filters, is dried, and obtains multi-functional phase-change material micro-capsule,
Its surface compact is smooth, with " core-shell structure copolymer " structure.Obtaining the phase transition temperature of the microcapsule through means of differential scanning calorimetry test is
32.8 DEG C and 39.2 DEG C, enthalpy of phase change is 154.9~155.3J/g；In light degradation experiment, after 140min solar irradiations, peafowl
Malachite green degradation rate is 80.46%；Tested by gas sensing property, after its result shows the microcapsule to the air-sensitive response of ethanol 3 times
Sensitivity does not decline, and its sensitivity is 1.37.
Embodiment 4
First by 2.4g AI3-28404,1.578g cetyl trimethylammonium bromide and 50mL water add three mouthfuls of 250mL
In flask, in 60 DEG C of oil bath pan, with the mechanical agitation speed emulsifying 1h of 300rpm.By the vinegar that 30mL concentration is 0.6mol/L
The 30mL concentration being configured is 2.5mol/L hydrogen after 1.5h in there-necked flask by sour copper solution fast drop
Sodium hydroxide solution and 30mL concentration are dropwise added drop-wise in there-necked flask for the glucose solution of 0.28mol/L, react 5h, stop stirring
Mix, 6~8h of ripening, then deionized water flushing product 3~5 times filters, is dried, and obtains multi-functional phase-change material micro-capsule,
Its surface compact is smooth, with " core-shell structure copolymer " structure.Obtaining the phase transition temperature of the microcapsule through means of differential scanning calorimetry test is
32.3 DEG C and 39.5 DEG C, enthalpy of phase change is 154.9~155.3J/g；In light degradation experiment, after 140min solar irradiations, peafowl
Malachite green degradation rate is 85.57%；Tested by gas sensing property, after its result shows the microcapsule to the air-sensitive response of ethanol 3 times
Sensitivity does not decline, and its sensitivity is 1.46.
Embodiment 5
First by 2.4g AI3-28404,1.578g cetyl trimethylammonium bromide and 50mL water add three mouthfuls of 250mL
In flask, in 60 DEG C of oil bath pan, with the mechanical agitation speed emulsifying 1h of 300rpm.By the sulfur that 30mL concentration is 0.5mol/L
The 30mL concentration being configured is 3.5mol/L hydrogen after 1.5h in there-necked flask by sour copper solution fast drop
Sodium hydroxide solution and 30mL concentration are dropwise added drop-wise in there-necked flask for the glucose solution of 0.28mol/L, react 5h, stop stirring
Mix, 6~8h of ripening, then deionized water flushing product 3~5 times filters, is dried, and obtains multi-functional phase-change material micro-capsule,
Its surface compact is smooth, with " core-shell structure copolymer " structure.Obtaining the phase transition temperature of the microcapsule through means of differential scanning calorimetry test is
31.7 DEG C and 38.2 DEG C, enthalpy of phase change is 133.7~135.2J/g；In light degradation experiment, after 140min solar irradiations, peafowl
Malachite green degradation rate is 83.26%；Tested by gas sensing property, after its result shows the microcapsule to the air-sensitive response of ethanol 3 times
Sensitivity does not decline, and its sensitivity is 1.55.
Embodiment 6
First by 2.4g AI3-28404,1.578g cetyl trimethylammonium bromide and 50mL water add three mouthfuls of 250mL
In flask, in 60 DEG C of oil bath pan, with the mechanical agitation speed emulsifying 1h of 300rpm.By the vinegar that 30mL concentration is 0.5mol/L
The 30mL concentration being configured is 2.5 after 1.5h in there-necked flask by sour copper solution fast dropH, stops
Only stir, 6~8h of ripening, then deionized water flushing product 3~5 times filters, is dried, and obtains multi-functional phase-change material micro-
Capsule, its surface compact is smooth, with " core-shell structure copolymer " structure.The phase alternating temperature of the microcapsule is obtained through means of differential scanning calorimetry test
Spend for 31.3 DEG C and 39.7 DEG C, enthalpy of phase change is 157.9~158.8J/g；In light degradation experiment, after 140min solar irradiations,
Malachite green oxalate degradation rate is 88.89%；Tested by gas sensing property, its result shows air-sensitive response of the microcapsule to ethanol 3 times
Sensitivity afterwards does not decline, and its sensitivity is 1.19.
Claims (10)
1. a kind of multi-functional phase-change material micro-capsule, it is characterised in that capsule core is organic phase change energy storage material, its species is to have
One or more in machine paraffin, higher aliphatic acids, senior class fatty alcohols and high-grade aliphatic ester class phase transformation energy storage material, glue
Softgel shell is Red copper oxide, and its structure is " core-shell structure copolymer " structure.
2. multi-functional phase-change material micro-capsule according to claim 1, it is characterised in that microcapsule entirety shared by capsule core
The mass percent of quality be 20~60wt.%, the mass percent of microcapsule total quality shared by capsule shells be 40~
80wt.%；Capsule grain diameter is 0.5~5.0 μm.
3. multi-functional phase-change material micro-capsule according to claim 1, it is characterised in that organic phase change material is organic calculus
One or more in wax, higher aliphatic acids, senior class fatty alcohols and high-grade aliphatic ester class phase transformation energy storage material.
4. multi-functional phase-change material micro-capsule according to claim 1, it is characterised in that capsule shells Red copper oxide capsule shells
Crystalline form be simple Emission in Cubic, and with ultraviolet light and visible light catalytic effect and gas-sensitive property.
5. prepare any one of claim 1-4 described in multi-functional phase-change material micro-capsule method, it is characterised in that include with
Lower technical process：(1) in the case where temperature is for 40~80 DEG C, by surfactant, matter that weight/mass percentage composition is 1.2~5.3wt.%
Amount percentage composition be 2.2~4.7wt.% organic phase change material and weight/mass percentage composition be 90.0~96.6wt.% go from
Sub- water mixing, stirs 1~3h under the rotating speed of 250~450rpm, obtains uniform and stable emulsion；(2) said temperature is being maintained
Under conditions of constant with stir speed (S.S.), copper source aqueous solution is added in the organic phase change material emulsion prepared by step (1), is made
1~3h of its reaction, then again while Deca sodium hydrate aqueous solution and reducing agent aqueous solution, after continuing 4~6h of reaction, stop stirring
Mix, 6~8h of ripening, be washed with deionized 3~5 times, spontaneously dry, that is, obtain multi-functional photograph and become material microcapsule product.
6. method according to claim 5, it is characterised in that the raw material composition and quality hundred of reaction system in step (2)
Point ratio is：
7. method according to claim 5, it is characterised in that described surfactant is cationic surface active agent
Or nonionic surfactant, wherein it is preferred that cetyl trimethylammonium bromide, Dodecyl trimethyl ammonium chloride, dodecyl
One or more in sodium sulfate, PVP, Polyethylene Glycol, span20, tween80.
8. method according to claim 5, it is characterised in that described reducing agent is ascorbic acid, hydrazine hydrate, glucose
With the one kind in sodium sulfite, the mass percent concentration of its aqueous solution is 3.3~14.3wt.%.
9. method according to claim 5, it is characterised in that described copper source is in Schweinfurt green, copper sulfate and copper chloride
One kind, the mass percent concentration of its aqueous solution is 6.2~13.8wt.%.
10. method according to claim 5, it is characterised in that the concentration of sodium hydrate aqueous solution is 2~4mol/L.
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